Chloroethylene polymers and salicyloxy hydroxy-benzophenones



Un t d S ates Patent CHLOROETHYLENE POLYMERS SALICYL- OXYHYDROXY-BENZOPHENONES "Gerald A. Clark, Midland, Mich assignor t r'heDow Chemical Company, Midland, Michl, a corporation or Delaware NoDrawing. Application A ril 23, 1956 Serial No. 579,75

3 Claims. (Cl: 260 -4535) I This invention relates to new organic;compounds and:

to polymeric compositions containing the same. ,More

particularly, it relates to new organiecompouhds'finding] P atented Aug.4,. 1959 illustrated by. the following preparation of salicylic acid:

(3-hydroxy-4-benzoyl) phenyl ester. Monobenzo'yl resorcinol was heatedat 40 mm. mercury with a slight excess of phenyl salicylate at atemperature of from 180' to 200 C. The phenol byproduct of the reactionwas continuously removed by distillation throughout the reaction. Thereaction product was purified by recrystallizautility as lightstabilizers for haloethyleiie polymers:-

Haloethylene polymers are known to bhighly sensitive 7 to the elfects ofelevated temperatures and of-lightandunder prolonged exposure to heatand light may become so degraded as to be commercially useless. It hasbeen common practice to blend certain compounds with the polymer tostabilize it against the degradative eifects of heat and light. Severalof such compounds, however, are colored materials which impart anobjectionable initial color to the stabilized composition and thusprevent the production of a commercially salable white composition.

Still other disadvantages of many of the previous compounds are a highodor level and volatility. Obviously, any odor in the stabilizer will betransferred to the stabilized composition. When volatile stabilizers areemployed the stabilizers volatilize out of the composition, leaving thecomposition in time unprotected against the degradative effects oflight, particularly ultra-violet light. In addition, all of thecompounds vary in their ability to absorb ultra-violet light and it isimpossible to predict the elfectiveness of any particular compound withany degree of certainty, and some of the compounds lose some of theirefiectiveness for absorbing ultra-violet light over a prolonged periodof time.

In view of the above problems it would be desirable and it is theprincipal object of the invention to provide a new group of organiccompounds useful for the stated purpose.

It is a further object to provide a polymeric haloethyl- 'enecomposition stabilized against the degradative effects of light by meansof such compounds.

It is a still further object to provide a group of such compounds whichhave little or no color and have a low odor level.

Another object is to provide a group of such compounds which have lowvolatility.

Other objects will become apparent as the description of the inventionproceeds.

The above and related objects are accomplished by means of a group ofcompounds having the general formula:

wherein X and Y are selected from the group consisting of H, Cl, Br, andalkyl; and Z is selected from the group consisting of salicylates andhydrocarbon substituted salicylates. As typical examples of compoundsthat are [tion from alcohol resulting in pale yellow crystals melting atl28;6--l28.7 C.-- Ina similar manner salicylic acid:[3-hydroxy-4-(2-chlorobenzoyl)] phenyl'ester was prepared resulting in awhite crystalline solid melting at 116- 117 C. The structures of thecompounds were confirmed by infra-red absorption and by chlorineanalysis where applicable. All of the compounds were found to be free ofany objectionable odor.

The compounds were evaluated as light stabilizers for haloethylenepolymers. Because of their low odor and color levels they producedcompositions which were more merchandisaole than compositions preparedfrom previous stabilizers. The effectiveness of the stabilizers will bemore apparent from the following illustrative example wherein all partsand percentages are by weight.

A series of samples was prepared from a basic formulation consisting of90.15 parts of a copolymer prepared from percent vinylidene chloride and15 percent vinyl chloride, 7 parts of a mixed tetraester ofpentaerythritol having fatty acid groups of C and C chain length, as aplasticizer, 0.5 part of sodium tripolyphosphate, 0.5 part of disodiumlauryl phosphate, 0.5 part of sorbiton monostearate, 0.3 part of citricacid, and 0.05 part of maleic anhydride as heat stabilizers andextrusion aids. One of the samples was left as a blank. To each of theothers was added a light stabilizer. The samples were molded intospecimens 0.01 inch thick and exposed to sun lamps until a standardamount of browning had been reached.

The specimens were also exposed to direct sunlight in the State ofArizona until a standard amount of browning had been reached. Theresults are listed in Table I.

These and other tests have shown the new compounds to be useful lightstabilizers for the various haloethylene polymers, including vinylidenechloride polymers and copolymers and vinyl chloride polymers andcopolymers. The most useful range of concentration of the new compoundsin such compositions is from 1 to 4 percent by weight.

2,898,323 a ii 1 r A 3 v v 4 Iclaim:

2. The composition claimed in claim 1 wherein said 1. A thermoplasticcomposition comprising a chlorocompound has the formula; ethylenepolymer and from 1 to 4 percent of a compound having the generalformula:

Cl OH i 5 0 on OH Q X 0 3. The composition claimed in claim 1 whereinsaid Y z 10 compound has the formula:

0 wherein X and Y are selected from the group consisting ll of hydrogen,chlorine, and bromine, and Z is selected C 0 OH from the groupconsisting of salicyloxy and aliphatic alkyl 15 O IJ Q substitutedsalicyloxy.

References Cited in the file of this patent UNITED STATES PATENTS2,157,068 Carruthers et a1 May 2, 1939 2,392,361 Britton et a1 Ian. 8,1946 2,445,739

Rowland et a1. July 20, 1948

1. A THERMOPLASTIC COMPOSITION COMPRISING A CHLOROETHYLENE POLYMER ANDFROM 1 TO 4 PERCENT OF A COMPOUND HAVING THE GENERAL FORMULA: